高介电常数BaTiO3陶瓷畴反转电流影响因素的研究

采用溶胶-凝胶结合二次煅烧的方法制备了高介电常数BaTiO3陶瓷,通过X射线衍射分析得到所制备的体系为四方相和立方相共存结构,从扫描电镜的图像中能观察其晶粒尺寸为1μm。通过TF2000铁电分析仪得到其介电常数在煅烧温度为1310℃,保温时间为4h,室温、测试频率为100Hz、测试电压为100V的条件下最大值为38306。研究了BaTiO3铁电陶瓷的反转电流随温度、频率和电压的影响规律,研究发现随着温度的升高反转电流缓慢降低,而随着电场和频率的增加反转电流迅速升高。从能量的观点也能进一步分析温度和电场对于反转电流的影响。     

Effects of Bi2O3 and Cr2Ti3O9 Co-doping on dielectric properties in BaTiO3-based ceramics

A microwave ceramic with general composition (1-x-y) BaTiO₃ + x Cr₂Ti₃O₉ + y Bi₂O₃ has been prepared by solid state synthesis at 1300-1400 °C. The phase composition, perovskite structural parameters and dielectric properties have been obtained by X-ray diffraction and dielectric measurements as a function of chemical composition and temperature. At low doping levels the formation of BaTiO₃-based solid solution has been found. The precipitation of BaCrO₃ has been detected at x = y = 2.0 mol%. A model of the incorporation of Cr³⁺ and Bi³⁺ ions into BaTiO₃-based crystal lattice has been proposed. Diffused phase transition in the temperature range 100-140 °C have been revealed by dielectric measurements for different ceramic composition. As high dielectric constant as 7311 and as low dielectric loss as 0.02 have been found for the composition of 0.98BaTiO₃-0.01Cr₂Ti₃O₉-0.01Bi₂O₃.     

Effects of lanthanum modification on electrical and dielectric properties of Pb(Zr0.70,Ti0.30)O3 ceramics

Lanthanum modified lead zirconate titanate ceramics with lanthanum content changing from 7.6 to 9.0 at.% La and a Zr/Ti ratio of 70/30 (PLZT 100x/70/30) have been prepared by conventional high temperature solid-state reaction technique. The studies of the ferroelectric, electromechanical and dielectric properties of the ceramics were carried out. The results showed the enhanced antiferroelectricity stability when the lanthanum content increases. The polarization and strain decreased with the increasing La content. The dielectric spectra of all the PLZT samples show a dispersive behavior. With increasing La concentration, the maximum dielectric constants ε_m and the transition temperatures T_m were reduced.     

Study on the microstructure and dielectric properties of X9R ceramics based on BaTiO3

This paper investigated the microstructure and dielectric properties of BaTiO₃-Pb(Sn, Ti)O₃ system ceramics. The Curie point of BaTiO₃ is 130 °C. When the temperature is higher than 130 °C, the dielectric constant of BaTiO₃ drops severely according to Curie-Weiss law. Pb(Ti, Sn)O₃(PTS) was selected to compensate the dielectric constant doping of BaTiO₃ since it has high Curie temperature (Tc) point that is about 296 °C. The Curie temperature (Tc) point of BaTiO₃ was broadened and shifted to higher temperature because of the doping of PTS, so the temperature coefficient of capacitance (TCC) curves of the ceramics based on BaTiO₃ was flattened. When 2 wt% Pb(Ti_0.55Sn_0.45)O₃ was added, the sample showed super dielectric properties that the dielectric constant was >1750 at 25 °C, dielectric loss was lower than 2.0% and TCC was <±10% from −55 °C to 200 °C. Therefore the materials satisfied EIA X9R specifications.     

Decrease of dielectric loss in giant dielectric constant CaCu3 Ti4 O12 ceramics by adding CaTiO3

CaCu₃ Ti₄ O₁₂–x CaTiO₃ ceramics (x=0,0.1,0.2,0.3,0.4 and 0.5) was studied by X-ray diffraction, scanning electron microscope and dielectric measurements. It was indicated that some CaTiO₃ entered the boundaries of CaCu₃ Ti₄ O₁₂ grains and/or subgrains. Dielectric measurement showed that the addition of CaTiO₃ lowered the dielectric loss remarkably, especially at low frequencies, while the giant dielectric constant still remained. At room temperature, the dissipation factor of the x=0.5 sample was decreased to 0.02 over the frequency range from 50 to 2000 Hz, and the dielectric constant was kept to be 4000. We explain this phenomenon in terms of internal barrier layer capacitance model by using the impedance spectroscopy analysis.     

Barrier layer and grain boundary effects in Nd/Zr doped BaTiO3 ceramics

Gradient structures with barrier layer characteristics and core-shell morphology have been developed in BaTiO₃ ceramics with Nd₂O₃ and ZrO₂ as co-dopants. Features include reduced Curie temperatures and anisotropic stress gradients, resulting from an oxidized surface layer and reduced interior, developed during air sintering. Co-doping was typically carried out through solution milling of the BaTiO₃ powders with nitrate precursors of the dopant oxides, spray drying and sintering of the pressed pellets in air ambient at 1300-1320 °C/60-90 min with furnace cooling. Structural characterization, as well as dielectric and d.c. resistance measurements of the pellets, as-sintered and after removing equal amounts of material from both surfaces, revealed the existence of an oxidized surface layer and barrier layer microstructures consisting of graded regions of oxidized insulating surfaces over partially oxidized or conducting grain interiors. In this complex structure, the ZrO₂ segregates to the grain boundary region, forming a core-shell structure, with Nd₂O₃ partitioning between the BaTiO₃ and ZrO₂ phases. The overall system was modeled in terms of an equivalent circuit and the analysis indicates that the dielectric constant and the loss behavior are strongly impacted by both the surface and grain boundary barrier characteristics, with the surface barrier effects having the more dominant effect on the dielectric properties of the doped compositions. Indications are that fine-tuning of the system to optimize the grain boundary effect could lead to extraordinary dielectric constant effects which could potentially be utilized in high energy storage devices.     

Microstructures and dielectric properties of CaTiO3–LaSrAlO4 composite ceramics

The microstructures and dielectric properties of xCaTiO₃/(1−x)LaSrAlO₄ composite ceramics were investigated. CaTiO₃ and LaSrAlO₄ could co-exist when the content of CaTiO₃ was no more than 30 mol%, while LaAlO₃ and CaO phases were observed in the composite ceramics with higher CaTiO₃ content. The dielectric constant of the composite ceramics increased with increasing the additive content, and the dielectric loss generally increased with increasing the additive content because of the presence of phase boundary and the high dielectric loss of the minor phases. The temperature coefficient of dielectric constant decreased with increasing the additive content firstly, and then it increased abnormally when x equals to 40 mol%, finally it decreased with increasing the additive content further. The dielectric properties predicted from serial formula were most close to those obtained from experiment among the classical dielectric mixture rules.     

Enhanced dielectric,ferroelectric and optical properties of lead free (K0.17Na0.83)NbO3 ceramic with WO3 addition

Polycrystalline lead-free ceramics (K_0.17Na_0.83)NbO₃ + x wt.% WO₃; (x = 0, 1, 3 and 5) have been synthesized via solid state reaction method. X-ray diffraction pattern at room temperature indicates the formation of pure perovskite phase with monoclinic structure for all samples. Dielectric constant versus temperature measurements shows an increase in dielectric constant with a shift in Curie temperature (T_C) toward higher temperature side. Remnant polarization (P_r) is found to be enhanced and reached upto 24 μC/cm² for x = 5 wt.% WO₃ from 12.5 μC/cm² for pure (K_0.17Na_0.83)NbO₃ ceramic. The value of coercive field (E_c) decreases with increasing wt.% of WO₃. From optical band gap study, we found blue shift in the band gap of (K_0.17Na_0.83)NbO₃ with increasing concentration of WO₃.     

Dy掺杂BaTiO3陶瓷的制备及其介电性能

采用溶胶凝胶法制备了掺杂不同量Dy2O3(掺杂摩尔分数分别为0.001,0.002,0.003,0.005,0.007)的BaTiO3陶瓷,并对其介电性能的变化进行了研究.结果表明Dy2O3掺杂使BaTiO3陶瓷的电阻率明显降低,当添加量为0.005mol时,电阻率最小,为4.19×108Ω·m.Dy2O3掺杂使BaTiO3陶瓷的介电性能在不同掺杂量和不同频率下发生了明显变化,掺杂量为0.001mol、0.002mol时,BaTiO3陶瓷的介电特性和频率特性得到明显改善,在频率为1000Hz时介电性能相对较好.Dy2O3掺杂使BaTiO3陶瓷的介电温谱有所展宽,且Curie温度有所降低,交流电导随着温度的升高而增大,并在Curie点附近达到最高.     

Sintering and dielectric properties of BaTiO3 prepared by a composite-hydroxide-mediated approach

High purity tetragonal BaTiO₃ powders consisted of uniform particles of ca. 150 nm in diameter were synthesized by a composite-hydroxide-mediated approach at 240 °C using a novel hydrothermal reaction apparatus with a rolling system. The product showed sinterability superior to the commercial powder, i.e., it could be sintered to full theoretical density at 1200 and 1100 °C without an additive and with 0.3 wt% of Li₂CO₃-0.04 wt% of V₂O₅ mixed sintering aid, respectively. The sintered body of the product also showed piezoelectric properties superior to the commercial one.     

Microwave dielectric properties of Li2TiO3 ceramics sintered at low temperatures

Li₂TiO₃ ceramics were prepared at the sintering temperatures from 1050 to 1250 °C. The optimal microwave dielectric properties were ?_r = 23.29, Q × f = 15,525 GHz (5.9 GHz), and τ_f = 35.05 ppm/ °C for the sample sintered at 1200 °C. The microwave dielectric properties were improved obviously when the Li₂TiO₃ ceramics were sintered at low temperatures with small additions of H₃BO₃ (B₂O₃ in the form of H₃BO₃). Only monoclinic Li₂TiO₃ was found in the pure or H₃BO₃-doped Li₂TiO₃ ceramics. About 1.0 wt.% H₃BO₃ addition aided the sintering of Li₂TiO₃ ceramics effectively while excessive H₃BO₃ (≥2.5 wt.%) was not favorable. Typically the best microwave dielectric properties were ?_r = 23.28, Q × f = 37,110 GHz (6.3 GHz), and τ_f = 30.43 ppm/ °C for the 1.0 wt.% H₃BO₃-doped Li₂TiO₃ ceramic sintered at 920 for 3 h, which is promising for LTCC applications.     

Low temperature sintering and microwave dielectric properties of SmAlO3 ceramics

The effects of sintering aids on the microstructures and microwave dielectric properties of SmAlO₃ ceramics were investigated. CuO and ZnO were selected as sintering aids to lower the sintering temperature of SmAlO₃ ceramics. With the additions, the sintering temperature of SmAlO₃ can be effectively reduced from 1650 to 1430°C. The crystalline phase exhibited no phase differences at low addition level while Sm₄Al₂O₉ appeared as a second phase as the doping level was over 0.5 wt.%. In spite of the additions, the dielectric constants showed no significant change and ranged 19-21. However, the quality factor Q×f was strongly dependent upon the type and amount of additions. The Q×f values of 51,000 and 41,000 GHz could be obtained at 1430°C with 0.25 wt.% CuO and ZnO additions, respectively. The temperature coefficients depended on the additions and varied from −40 to −65 ppm/°C. Results of X-ray diffractions, EDS analysis and scanning electron microscopy were also presented.     

Modified tunable dielectric properties by addition of MgO on BaZr0.25Ti0.75O3 ceramics

Phase composition, microstructure and tunable dielectric properties of (1 − x)BaZr_0.25Ti_0.75O₃-xMgO (BZTM) composite ceramics fabricated by solid-state reaction were investigated. It was found Mg not only existed in the matrix as MgO, there was also trace amount of Mg²⁺ ions dissolved in the BZT grains, which led to Curie temperature of the BZTM composites ceramics shifting to below −100 °C. Dielectric permittivity of the BZTM composite ceramics was reduced from thousands to hundreds by manipulating the content of MgO. Johnson's phenomenological equation based on Devonshire's theory was used to describe the nonlinear dielectric permittivity of the ceramics with increasing applied DC field. With increasing content of MgO, anharmonic constant α_(T) increased monotonously. Dielectric permittivity was 672, while dielectric tunability was as high as 30.0% at 30 kV/cm and dielectric loss was around 0.0016 for the 0.6BaZr_0.25Ti_0.75O₃-0.4MgO sample at 10 kHz and room temperature.     

Effects of Ca and Zr substitution upon structure and properties of Ba5LaTi3Ta7O30 low-loss dielectric ceramics

Effects of Ca and Zr substitution upon the dielectric properties of Ba₅LaTi₃Ta₇O₃₀ ceramics were investigated together with the structural characterization. All the samples of Ba₅La(Zr_xTi_1−x)₃Ta₇O₃₀ formed a filled tungsten-bronze structures, whereas the solid solution limit was determined as x=0.25 in (Ca_xBa_1−x)₅LaTi₃Ta₇O₃₀. Beyond this limit secondary phase of CaTa₂O₆ was detected and it would become the major phase for the Ca-rich compositions. The temperature coefficient of dielectric constant was improved with increasing Zr content while the dielectric constant decreased and the low dielectric loss varied little (in the order of 10⁻⁴). In the case of (Ca_xBa_1−x)₅LaTi₃Ta₇O₃₀, small temperature coefficient of dielectric constant could be obtained with increasing Ca content while the dielectric constant decreased significantly, and a small amount substitution of Ca for Ba induced decrease in dielectric loss.     

Crystal structure of dense nanocrystalline BaTiO3 ceramics

The dense nanocrystalline BaTiO₃ ceramics with the average grain size of 30 nm was sintered by the pressure assisted method. The Raman spectroscopy and the Rietveld refinement were employed to characterize the structural information of the nanocrystalline BaTiO₃ ceramics. The structural parameters and the reliability factors for the nanocrystalline BaTiO₃ ceramics were successfully determined by the Rietveld refinement based on the analysis of Raman spectra. A multiphase coexistence of tetragonal and orthorhombic phases was observed in 30 nm BaTiO₃ ceramics at room temperature. The phenomenon can be explained by the internal stress.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

Effect of Sn2O3 doping on structural,optical and dielectric properties of ZnO ceramics

The synthesis of the undoped ZnO and ZnO–Sn₂O₃ composites prepared by conventional solid-state reaction method has been reported. Besides, the effect of increasing Sn₂O₃ content from 5 to 15 wt% on structural, optical, dielectric and electrical properties of the ZnO–Sn₂O₃ composites has also been investigated. In fact, the X-ray diffraction analysis indicates that the as-prepared ZnO–Sn₂O₃ composites may contain some combined phases such as SnO and Zn₂SnO₄. The atomic force microscopy shows that the surfaces of the composites are rough. The band gap energy seems to depend on the amount of Sn₂O₃ addition, with the maximum obtained at 15 wt% Sn₂O₃. Concerning the optical band gap, it has been found to be in the range of 3.18–3.93 eV. The dielectric loss was found to decrease with the increase in frequency. The results obtained from the ac-conductivity revealed that the values of σ(ω) increases with the Sn₂O₃ adding content. The dc-conductivity of all the composites increases with the increase in temperature. The electrical conductivity was analyzed with the power law, and agrees with the correlation barrier hopping model.     

Microstructure and microwave dielectric properties of (1 − y)Li3NbO4+yLi2TiO3(Li2SnO3) ceramics

Phase formation, microstructure and microwave dielectric properties of (1 − y)Li₃NbO₄ + yLi₂TiO₃(Li₂SnO₃) ceramics have been studied in this paper. The structure and microstructure of the compounds were investigated using X-ray powder diffractometer (XRD), scanning electron microscope (SEM), Raman spectrometer. The microwave dielectric properties of the ceramics were studied with a network analyzer at the frequency of about 8–12 GHz. Li₃NbO₄ formed ordered solid solutions with the addition of small amount of Li₂TiO₃ (y ≤ 0.2), whereas no solid solution formed with the addition of small amount of Li₂SnO₃. Small amount of Li₂TiO₃ doping suppressed the appearance of impurity phases caused by lithium evaporation for Li₃NbO₄. The Li₂TiO₃ doped compositions with 0.02 ≤ y ≤ 0.08 demonstrated homogeneous and dense microstructure after sintering at 1150 °C/2 h, in contrast the 0.2 ≤ y ≤ 0.6 specimens exhibited porous and subgrains microstructure after sintering at 1250 °C/2 h. Short range ordering was observed in the 0.2 ≤ y ≤ 0.6 compositions. Mechanical mixture phases of Li₃NbO₄ and Li₂SnO₃ based solid solution (Li₂SnO₃ (ss)) existed in the Li₂SnO₃ added specimens_. The dielectric permittivity increased with increasing Li₂TiO₃ addition, but decreased with the increase of Li₂SnO₃ content. All specimens exhibited negative τ_f value for the Li₂TiO₃ added specimens, although its absolute τ_f value decreased with the increase of Li₂TiO₃ addition. Whereas, the τ_f value changed from negative into positive with the increase of Li₂SnO₃ addition. Optimized combined microwave dielectric properties (?_r = 19.8, Q × f = 91,200 GHz, τ_f = −24 ppm/°C and ?_r = 16, Q × f = 75,300 GHz, τ_f = 3 ppm/°C) could be obtained for the Li₂TiO₃ added (y = 0.6) and Li₂SnO₃ added specimens(y = 0.7), respectively. The microwave dielectric properties of the Li₂SnO₃ end member are ?_r = 13.5, Q × f = 61,600 GHz, τ_f = 29 ppm/°C.     

Influence of ZnO additions to 0.8(Mg0.95Co0.05)TiO3–0.2Ca0.6La0.8/3TiO3 ceramics on sintering behavior and microwave dielectric properties

The effects of ZnO addition on the microstructures and microwave dielectric properties of 0.8(Mg_0.95Co_0.05)TiO3–0.2Ca_0.6La_0.8/3TiO₃ ceramics were investigated. ZnO was selected as liquid phase sintering aids to lower the sintering temperature of 0.8(Mg_0.95Co_0.05)TiO3–0.2Ca_0.6La_0.8/3TiO₃ ceramics. With ZnO additives, the densification temperature of 0.8(Mg_0.95Co_0.05)TiO₃–0.2Ca_0.6La_0.8/3TiO₃ can be effectively reduced from 1450 to 1200–1325 °C. The crystalline phase exhibited no phase difference at low addition levels (0.25–2 wt.%). It is found that low-level doping of ZnO (0.25–2 wt.%) can significantly improve the density and dielectric properties of 0.8(Mg_0.95Co_0.05)TiO₃–0.2Ca_0.6La_0.8/3TiO₃ ceramics. The quality factors Q × f were strongly dependent upon the amount of additives. Q × f values of 36 000 and 13 000 GHz could be obtained at 1200–1325 °C with 1 and 2 wt.% ZnO additives, respectively. During all additives ranges, the relative dielectric constants were significantly different and ranged from 23.1 to 27.96. The temperature coefficient varies from 14.1–24.3 ppm/°C.